CN100551447C

CN100551447C - Comprise powdery, water-absorbent polymers by means of the agglutinating fine particle of thermoplastic adhesives

Info

Publication number: CN100551447C
Application number: CNB2004800215493A
Authority: CN
Inventors: F·勒克尔; H·布伦穆斯; S·史密斯
Original assignee: 施拖克豪森有限公司
Current assignee: Evonik Super Absorbent Co ltd
Priority date: 2003-07-25
Filing date: 2004-07-22
Publication date: 2009-10-21
Anticipated expiration: 2024-07-22
Also published as: CN1845763A; US20070066754A1; EP1648603A2; US20110015601A1; US8518541B2; US7842386B2; US20130001468A1; US8288002B2; BRPI0412852A; JP2006528544A; WO2005011860A2; EP1648603B1; KR20060059983A; JP4829786B2; KR101044581B1; WO2005011860A3; BRPI0412852B1; DE10334286A1; DE10334286B4; TW200523017A

Abstract

The present invention relates to powdery, water-absorbent polymers, it comprises: the particle diameter of 0.01-20wt% is the water-absorbing polymeric particles of at least 200 μ m less than fine particle, the thermoplastic adhesives of 0.001-10wt%, the 60-99.998wt% particle diameter of 200 μ m.Described fine particle is bonded on the surface of described water-absorbing polymeric particles by described thermoplastic adhesives.Described powdery, water-absorbent polymers has the flow valuve (FFC) of 1-13 or is at most 6 dust ratio.The purposes of powdery, water-absorbent polymers, transmission method, complex, chemicals and the thermoplastic adhesives that disclose the preparation method of powdery, water-absorbent polymers in addition, obtained by this method.

Description

Comprise powdery, water-absorbent polymers by means of the agglutinating fine particle of thermoplastic adhesives

The present invention relates to powdery, water-absorbent polymers, preferred superabsorbents; The method for preparing powdery, water-absorbent polymers; By the available powdery, water-absorbent polymers of this method; Carrying method; Complex; The purposes of chemicals and thermoplastic adhesives.

Superabsorbents is water-insoluble cross linked polymer, and it can be by swelling and forms that hydrogel absorbs and keep a large amount of water, liquid, aqueous, especially body fluid, preferably urine or blood under pressure.Superabsorbents absorbs 100 times of preferred himself weight at least in water.About the more details of superabsorbents at " Modern Superabsorbent Polymer Technology ", F.L.Buchholz, A.T.Graham, Wiley, VCH is described in 1998.Because these characteristic properties, these water absorbent polymers mainly are added in the hygienic articles, for example baby diaper, incontinence article or sanitary towel.

The superabsorbents that can buy is crosslinked polyacrylic or crosslinked starch-acrylic acid-grafted polymer class basically at present, and wherein said carboxyl is partly neutralized by sodium hydroxide or potassium hydroxide.These can obtain by free yl polymerizating monomer acrylic acid in the presence of suitable crosslinking method or its corresponding salt.In this process, can adopt different polymerizations, for example polymerisation in solution, emulsion polymerisation or suspension polymerisation.At last, obtain water absorbent polymer with the particulate form of particle diameter 150-850 μ m, subsequently it is joined in the hygienic articles by these diverse ways.

For absorption and the swelling ability of improving these water-absorbing polymeric particles, many methods of wherein the polymer beads surface being carried out modification have been narrated.For example, known by DE-A-40 20 780 transforming described water-absorbing polymeric particles with the alkaline carbon acid esters of the carboxyl reaction of polymer beads.The surperficial secondary cross-linking of Shi Xianing can cause polymer Absorption under pressure to increase by this way.

Except making that with reactive compounds described polymer beads transforms, many methods have also been described in the prior art, with the performance of the described water-absorbing polymeric particles of these methods by realizing with inorganic or organic fine particle coating.

Thereby in DE-A-35 03 458, described superabsorbent particles absorbability, absorption rate and gel stability can by in the presence of the secondary cross-linking agent, use the inert inorganic dusty material for example silicon dioxide be improved.For the hygroscopicity that reduces polymer beads and reduce its caking thus, EP-A-0 388 120 has proposed the voluminous powder coated polymer particles with high-purity silicon dioxide, and wherein this powder has mean diameter and the 500m of 0.1-30 μ m ²The specific surface area of/g.

DE-A-199 39 662 has instructed with granular cyclodextrin and zeolite and has applied water-absorbent polymer structure, so that thus in conjunction with having the chemical compound from body fluid that makes us unhappy abnormal smells from the patient.

Common problem is that it can cause discharging the fine particle that is dust form in the method for all these follow-up modifications, wherein these fine particles produce by mechanical stress, as by as described in the pneumatic conveying of water-absorbing polymeric particles and the wearing and tearing of the occasionality on it, perhaps owing to be used for inorganic or organic fine particle that the follow-up modification of polymer beads applies to the surperficial insufficient adhesive attraction of absorbent fine particle.

Dust, especially particle diameter discharge because the cause of toxicity on inhalation is undesirable less than the dust of 10 μ m; Particle diameter can cause having the visible dust of its all after effects (after-effect) less than the fine particle of 100 μ m and cause producing and the handling problem of processing in distributing.The most important thing is that the flowability in the surface with the superabsorbents of inorganic or organic granular modification can be subjected to the negative effect of these granules at the not enough adhesive attraction of described superabsorbent particles surface.

Purpose of the present invention thereby be to overcome the shortcoming that occurs in the prior art.

Especially, the object of the present invention is to provide a kind of method that can prepare with the superabsorbent particles of inorganic or organic granular modification, described superabsorbent particles has the enough adhesive attraction of described inorganic or organic granular to this superabsorbent particles surface.

In addition, the object of the present invention is to provide for example with regard to absorbability, permeability or absorption rate, have superb absorbency can absorbent particle, and its conveying in being used for preparing the transporter of hygienic articles has gratifying flow behavior and is not inclined to the formation dust.

In addition, one object of the present invention is to provide the water-absorbing polymeric particles that for example has the superb absorbency energy with regard to absorbability, permeability or absorption rate, it is characterized in that favorable mechanical stability in addition.

In addition, described water-absorbing polymeric particles should be by described water-absorbing polymeric particles to the adhesive attraction of described matrix fiber and fully fixing in this complex when it joins in the complex that comprises fibrous material substrate.

Another purpose of the present invention is to provide the complex that comprises water-absorbing polymeric particles, described complex has and the suitable at least water absorption of prior art known absorption granule by means of the superb absorbency energy of described water-absorbing polymeric particles, perhaps can realize described water-absorbing polymeric particles gratifying fixed effect in this complex in this complex, the water-absorbing polymeric particles that joins thus in this complex has the tendency of the formation dust of improved stability and/or reduction.

One object of the present invention further is to provide the chemicals that comprises described water-absorbing polymeric particles, and these goods have excellent absorption properties and it is characterized in that alap dust discharges, for example in the mechanical stress process.

In addition, one object of the present invention is to provide water-absorbing polymeric particles, its by in the course of conveying in producing these polymer beads or the degree that suffers damage of the mechanical requirements that occurs during the further course of processing in the quantitative system in air lay or rhombus weavy grain (diaper) machine as far as possible little and form the least possible dust.Above-mentioned purpose by according to the powdery, water-absorbent polymers that forms respective classes claim, prepare powdery, water-absorbent polymers method, solve by the purposes of the available powdery, water-absorbent polymers of this method, carrying method, complex, chemicals and thermoplastic adhesives.According to powdery, water-absorbent polymers of the present invention or according to the favourable embodiment of the method for these powdery, water-absorbent polymers of preparation of the present invention is the theme of dependent claims, its correspondingly independent utility or combination mutually by any way.

Powdery, water-absorbent polymers of the present invention comprises as composition:

-0.01-20wt%, preferred 0.05-15wt% and even more preferably having of 0.1-10wt% less than 200 μ m, preferably less than 100 μ m and especially preferably less than the fine particle that passes through the particle diameter that screen analysis measures of 50 μ m;

The thermoplastic adhesives of-0.001-10wt%, preferred 0.01-5wt% and preferred especially 0.1-1wt%,

The water-absorbing polymeric particles of the particle diameter that passes through screen analysis mensuration of-60-99.998wt%, preferred 70-99wt% and preferred especially 80-95wt% with at least 200 μ m, preferred at least 250 μ m and preferred especially at least 300 μ m, mentioned component adds up 100wt%

Wherein

Described fine particle is bonded to the surface of described water-absorbing polymeric particles by described thermoplastic adhesives, and described powdery, water-absorbent polymers has

Be in 1-13, preferred 3-9, preferred especially 4-8 even the more preferably flow valuve according to test determines as herein described (FFC value) in the scope of 5-7, or

At the most 6, preferred at the most 4, preferred especially 2 dust ratio at the most according to test determines as herein described.Preferably, described powdery, water-absorbent polymers granule has flow valuve (FFC value) and the dust ratio in the above-mentioned scope.

According to an embodiment of the invention, these fine particles are the conveyings in producing superabsorbents and process for preparation or sieve the so-called superabsorbents fine particle that produces in the step.

In another embodiment of the present invention, preferred described fine particle is not superabsorbents and especially is not based on water absorption, crosslinked, the neutral polyacrylic of part or its salt.Therefore, for example, cyclodextrin is used as fine particle is used for hygienic articles in described preparation abnormal smells from the patient control, as narrating among EP 0,691 856 B1.

The preferred fine particle that is not based on water absorption, crosslinked, the neutral polyacrylic of part or its salt preferably is different from the organic fine particle or the inorganic fine particle of described water absorbent polymer.

As for organic material, any organic material granule well known by persons skilled in the art can be contained in the powdery, water-absorbent polymers of the present invention, and it is generally used for improving the performance of water absorbent polymer.Cyclodextrin or derivatives thereof and polysaccharide belong to described preferred organic fine particle.In addition, cellulose and cellulose derivative for example CMC, cellulose ether are preferred.

As for cyclodextrin or cyclodextrin derivative, it is preferred being disclosed in those chemical compounds that DE-A-198 25 486 page 3 the 51st walk in page 3 the 61st row.The above-mentioned part that is cited of the disclosure patent application is incorporated herein by reference and form the part of the disclosure of invention.The deutero-α of particularly preferred cyclodextrin right and wrong, β, γ or δ-cyclodextrin.In the use of organic fine particle preferred especially these fine particles with the amount of 0.1-1wt%, more preferably 0.25-0.75wt% amount and even more preferably the amount of 0.4-0.6wt% be contained in the described powdery, water-absorbent polymers.It is particularly preferred that the usage ratio that provides in the embodiment of the invention demonstrates.

As for inorganic material, any inorganic material particle of those skilled in the art's unanimity can be contained in the powdery, water-absorbent polymers of the present invention, and it is generally used for improving the performance of water absorbent polymer.Silicate, the silicate for example zeolite or the silicate that obtains by dring silicon aqueous acid or Ludox that especially form skeleton, for example commercially available product that gets such as precipitated silicate and pyrolysismethod silicic acid, for example have 5-50nm, the aerosol of preferred 8-20nm particle diameter such as " Aerosil 200 " of Degussa AG, aluminate, titanium dioxide, zinc oxide, other mineral materials that clay material and those skilled in the art use always and carbon containing inorganic material belong to preferred inorganic fine particle.

Preferred silicate is at " Holleman and Wiberg ", Lehrbuch derAnorganischen Chemie, Walter de Gruyter Verlag, 91.-100.1985 version " in the 750-783 page or leaf as disclosed all the natural or synthetic silicates of silicate.The above-mentioned part of this textbook is incorporated herein by reference and form the part of the disclosure of invention.

Particularly preferred silicate is zeolite.As for zeolite, all synthetic or natural zeolites well known by persons skilled in the art all can use.Preferred natural zeolite is the zeolite from sodalite class, harmotome class, modenite class, chabasie class, faujasite class (sodalite class) or analcime class.The example of natural zeolite is an analcime, leucite, pollucite, wairakite, Bel's Burger stone, silicon lithium aluminum stone, Burgers stone, brewsterite, chabasie, offretite, cowlesite, dachiardite, antiedrite, epistilbite, erionite, faujasite, ferrierite, amicite, garranite, zeagonite, dagger-axe silicon sodium aluminum stone, sodium chabazite, gonnardite, goosecreekite, harmotome, phillipsite, wellsite, clinoptilolite, heulandite, laumontite, levyine, mazzite, merlinoite, the Meng Tesuo horse, modenite, mesolite, sodalite, scolecite, offretite, secondary sodalite, paulingite, Perlialite, the plate zeolite, foresite, stellerite, karphostilibite, Tschernichite or yugawaralite.Preferred synthetic zeolite is zeolite A, X zeolite, zeolite Y, zeolite P or product A BSCENTS.

As for zeolite, can use the zeolite of what is called " middle (" mittlere ") " type, wherein SiO ₂/ AlO ₂Ratio is less than 10, preferably the SiO of these zeolites ₂/ AlO ₂Ratio is 2-10.Except these " centre " zeolites, also can use the zeolite of " high (" hohe ") " type, belong to wherein be for example to belong to known ZSM type " molecular sieve " zeolite and β zeolite.These " height " zeolites preferably have at least 35 SiO ₂/ AlO ₂Ratio, the SiO of preferred especially 200-500 ₂/ AlO ₂Ratio.

As for aluminate, the spinelle that uses occurring in nature to exist, especially common spinelle, gahnite, hercynite or picotite.

Preferred titanium dioxide is the pure titinium dioxide that is rutile, anatase and brockite crystal form, and iron content titanium dioxide ilmenite for example, and calcic titanium dioxide is sphene or perovskite for example.

Preferred clay material is those that describe as clay material in " Holleman and Wiberg, Lehrbuch derAnorganischen Chemie, Walter De Gruyter Verlag, 91.-100., 1985 editions " 783-785 page or leaf.The above-mentioned part of this textbook is incorporated herein by reference and form the part of the disclosure of invention.Particularly preferred clay material is kaolinite, illite, galapectite, Montmorillonitum and Talcum.

In addition, single, oligomeric-and the slaine of polyphosphoric acid type preferably as inorganic fine particle of the present invention.Wherein, especially preferred described hydrate, monohydrate to decahydrate and trihydrate is particularly preferred.As for metal, especially consider alkali metal and alkaline-earth metal, wherein alkaline-earth metal is preferred.Wherein, preferred Mg and Ca, preferred especially Mg.About phosphate, phosphoric acid and metallic compound thereof are referring to " Holleman and Wiberg, Lehrbuch der Anorganischen Chemie, Walter De Gruyter Verlag, 91.-100.1985 version " 651-669 page or leaf.The above-mentioned part of this textbook is incorporated herein by reference and form the part of the disclosure of invention.

The preferred non-organic material of carbon containing is those pure carbons of mentioning as graphite in the 705-708 page or leaf at " Holleman and Wiberg; Lehrbuch derAnorganischen Chemie; Walter De Gruyter Verlag, 91.-100.Edition, 1985 ".The above-mentioned part of this textbook is incorporated herein by reference and form the part of the disclosure of invention.Particularly preferred graphite is for example coke, pyrolytic graphite, active carbon or coal smoke of Delanium.

The fine particle that is contained in the powdery, water-absorbent polymers of the present invention can exist with fiber, foam or particle form, wherein optimum fiber and granule and special preferred particulates.If organic polysaccharide, for example cellulose fine particle are used as described fine particle, so preferred this fine particle preferably uses with fibers form.These fibers preferably have the line density of 0.5-6, preferred especially 0.7-4detex.The more details of suitable fibers are disclosed in EP-A-0 273 141.

In the use of described below organic or inorganic fine particle or its mixture, preferred especially these fine particles with 0.1-1wt%, more preferably 0.25-0.75wt% and even more preferably the amount of 0.4-0.6wt% be contained in the powdery, water-absorbent polymers.It is particularly advantageous that the ratio that provides in the embodiment of the invention demonstrates, especially for the organic and inorganic individualized compound of above detailed description.

In a preferred implementation of powdery, water-absorbent polymers of the present invention, these comprise the mix ingredients of organic and inorganic fine particle.

In a preferred implementation of powdery, water-absorbent polymers of the present invention, the fine particle that preferably is not based on water-absorbent crosslinked poly-(methyl) acrylate comprises inorganic fine particle and reaches 80wt% at least, preferably 90wt% and more preferably 95wt% at least at least are respectively in the weight of the fine particle that preferably is not based on water-absorbent crosslinked poly-(methyl) acrylate.

In another preferred implementation of powdery, water-absorbent polymers of the present invention, preferably do not comprise organic fine particle and reach 80wt% at least based on the water-absorbent crosslinked fine particle that gathers (methyl) acrylate, preferably at least 90wt% and even more preferably 95wt% at least, respectively in described preferably not based on the weight of the fine particle of water-absorbent crosslinked poly-(methyl) acrylate.

According to the present invention further preferably, described preferred do not have the 30-850m of being in based on the fine particle of water absorption, crosslinked, the neutral polyacrylic of part or its salt ²/ g, preferred 40-500m ²/ g, especially preferred 100-300m ²/ g and even more preferably 150-250m ²Specific surface area in the/g scope according to BET method mensuration.Usually, and be under sipernate and the aerocolloidal situation at described fine particle, its surface is 30-850m ²/ g, preferred 40-500m ²/ g, especially preferred 100-300m ²/ g and measure in area flowmeter with nitrogen according to ISO 5794 adnexa D.In a preferred implementation of powdery, water-absorbent polymers of the present invention, at least 90wt%, preferred 95wt% at least and even more preferably at least the preferred of 99wt% do not have less than 200 μ m, especially preferably less than 100 μ m and be more preferably less than 1 μ m and even be more preferably less than 500nm and further preferably less than the particle diameter of 100nm based on the fine particle of water-absorbent crosslinked polyacrylate.Sipernate has the particle diameter of 10-180 μ m, preferred 20-150 μ m and preferred especially 30-110 μ m.This particle diameter can be measured with Multisizer according to ASTM C 690-1992.In another embodiment of the present invention, sipernate has the mean diameter of 1-40 μ m, preferred 2-30 μ m and preferred especially 3-20 μ m when measuring according to ASTM C 690-1992.

With regard to " thermoplastic adhesives ", preferably be interpreted as the material that does not have adhesive property below the fixed temperature giving according to the present invention.Giving more than the fixed temperature, preferably more than the fusing point of this material, material shows adhering performance or adhesive property, and these performances still keep under curdled appearance after with the molten condition bonding two substrates.Preferably, corresponding viscosity or adhesive property are at more than the fusing point of measuring by differential scanning calorimetry (DSC) as the described material or the material blends of thermoplastic adhesives at least 10 ℃, preferably at least 20 ℃ and especially preferably show under 21-100 ℃.Also can use the thermoplastic adhesives that comprise two or more different chemical compounds among the present invention.Described two or more chemical compounds can be different aspect chemical composition or its molecular weight or this two.

Described thermoplastic adhesives preferably use as granule.In these granules, preferred 50wt% at least and the preferred especially granule of 70wt% at least have and are in 10-500 μ m, preferred 25-250 μ m and the more preferably particle diameter in the 40-120 mu m range.Described particle diameter can pass through the screen analysis of 20 μ m sizes at the most and determine.For particle diameter, can use light scattering to determine particle diameter less than 20 μ m.

As for thermoplastic adhesives, it is normally suitable greater than the polymeric material of about 1000g/mol molecular weight to have, it has corresponding fusion temperature and can not decompose or show any molecular change under corresponding serviceability temperature, otherwise this is disadvantageous for bond effect.

It is about 10 that the number-average molecular weight (Mn) that the described polymer that can be used as thermoplastic adhesives is measured by gel permeation chromatography (GPC) is preferably, and 000-about 1,000,000, especially preferred about 20,000-about 300,000 and even more preferably from about 50,000-is about 150,000g/mol.

Measure as passing through gel permeation chromatography (GPC) equally, the molecular weight distribution of described polymer can be unimodal.Randomly, the polymer that can be used as thermoplastic adhesives also can have bimodal or senior peak and distributes.

The chemical compound that can be used as thermoplastic adhesives among the present invention comprises respectively in the gross weight of described thermoplastic adhesives and has the 60wt% at least of following fusion temperature, preferred 80wt% at least and the more preferably part of 100wt% at least: its fusion temperature according to ISO 11357 be at least 50 ℃, preferably at least 60 ℃ and even more preferably at least 70 ℃, wherein preferably be no more than 300 ℃, especially preferably be no more than 250 ℃ and even more preferably no more than 200 ℃ according to the fusion temperature of ISO 11357.

Under up to about 30 ℃ temperature, however preferably be higher than under the temperature of this temperature, for example up to 40 ℃ or under up to 50 ℃, the thermoplastic adhesives that can be used among the present invention not only should be solids but also should have inviscid surface.

During a little more than described fusion temperature, described thermoplastic adhesives should have low relatively viscosity.Preferably, they should be less than 2 160 ℃ of melt viscosities with the 27# ingot according to Brookfield (ASTM E 28), 000Pas, and preferably less than 1,200Pas and especially preferably less than 600Pas.

As for thermoplastic adhesives, the preferred material with following feature that uses among the present invention: it comprises respectively in the gross weight of these thermoplastic adhesives 10wt% at least, preferred 50wt% at least and preferred especially 90wt% at least are selected from polyurethane, polyester, polyamide, polyolefin, polyvinylesters, polyethers, polystyrene type, polyimides is Polyetherimide especially, sulfur-containing polymer is polysulfones especially, polyacetals is polyformaldehyde especially, the fluoride plastics are Kynoar especially, styrene-olefin copolymer, the polymer of polyacrylate or vinyl-vinyl acetate copolymer or two or more above-mentioned mixture of polymers, in these polymer condensation polymer and wherein polyester be particularly preferred.

As for polyurethane, be understood that to have in the polymer backbone all polymer of at least two carbamate groups among the present invention.

As for polyurethane, all thermoplastic polyurethanes known to the skilled in polyurethane chemistry field are fit in the present invention, especially are generally used for preparing in thermoplastic forming body, the particularly film or are used for the polyurethane of thermoplastic coating on surface.For example, the PAUR or the EU that can obtain in the following manner are fit to: with corresponding polyfunctional alcohol especially two functional alcohol, for example two functional polyethers for example poly(ethylene oxide) make dicarboxylic acids change into polyethers-or PEPA, then with two or the polyfunctional isocyanate make corresponding polyethers-or PEPA transform.Particularly preferred thermoplastic polyurethane is by Kern GmbH company, Gro β meischeid, those polyurethane that Germany sells with product code " TPUD ", " TPU 93 A ", " TPU 80 A " and " TPU GF 20 ".Another preferred thermoplastic polyurethane is by Schaetti AG company, Zurich, and Switzerland is with product code The polyurethane of selling with production number " 6005 ".

As for polyester, be appreciated that all polymer that have at least two ester groups in the polymer backbone and do not have carbamate groups among the present invention.As polyester, all thermoplastic polyesters well known by persons skilled in the art all are fit in the present invention, especially are generally used for preparing in thermoplastic forming body, the especially film or are used for the polyester of thermoplastic coating on surface.For example, can by with corresponding polyfunctional alcohol especially two functional alcohol, for example two functional polyethers for example the poly(ethylene oxide) polyester that makes dicarboxylic acids transform to obtain be fit to.Wherein, the polyester of being made up of p-phthalic acid or derivatives thereof, M-phthalic acid or derivatives thereof, adipic acid or M-phthalic acid or derivatives thereof, adipic acid or derivatives thereof and at least a polyhydric alcohol, preferred butanediol or ethylene glycol or its mixture is preferred.In the embodiment of described ester, preferably p-phthalic acid or derivatives thereof, M-phthalic acid or derivatives thereof or their mixture account for the amount of 30-80wt% and the amount of preferred 40-65wt% in this ester.Another embodiment of described ester comprises the adipic acid or derivatives thereof with the amount of 3-20wt% and the amount of preferred 5-15wt%.In addition, another embodiment of described ester comprises at least a polyhydric alcohol, preferred butanediol or ethylene glycol or its mixture with the amount of 25-55wt% and the amount of preferred 30-40wt%.Above-mentioned wt% amount is based on corresponding ester all the time.

Particularly preferred thermoplastic polyester is by Kern GmbH company, Gro β maischeid, those polyester that Germany sells with product code " PET ", " PBT ", " PBT V 0 ", " PC ", " PC V 0 ", " PC FDA ", " PC GF 10 V0 " and " PC GF 30 ".Particularly preferably be company in addition by Schaetti AG, Zurich, Switzerland is with product code " SchaettiFix " those polyester as sale under production number " 373 ", " 374 ", " 376 ", " 386 ", " 386F " and " 399 ".Also preferably by Degussa AG company, the Dusseldorf, Germany is with the thermoplastic copolyesters of product code " Dynacoll 7000 ", " Dynacoll 7380 ", " Dynacoll 7340 ", " Vestamelt 4280 ", " Vestamelt 4481 ", " Vestamelt 4580 " and " Vestamelt4680/4681 " sale.

As for polyamide, among the present invention, can be fit to by make suitable two or polybasic carboxylic acid transform all plastic polyamides that obtain with corresponding amine.Among one of the present invention preferred embodiment, use to the polyamide of small part by making as dicarboxylic acids with dimer (fatty acid) yl.The present invention another preferred embodiment in, nylon-type is used as hot-melt adhesive, nylon-6 for example, 6, nylon-6,9 or nylon-6,12.

Particularly preferred polyamide thermoplastic is by Kern GmbH company, Gro β maischeid, Germany with product code " PA 6 E ", " PA 6 ", " PA 6 flex ", " PA 6 V 0 ", " PA6 MoS2 ", " PA 6 M 30 ", " PA 6 M 30 V 0 ", " PA 6 G 210 ", " PA6 G 210 H ", " PA 6 G 212 ", " PA 6 G 216 ", " ", those polyamide of selling of " PA6 G 210 AX ", " PA 6 G 210 MoS2 ", " PA 6 G 210 AX ", " PA 66 E ", " PA 66 ", " PA 66 H ", " PA 66 PE ", " PA 6/6T ", " PA 12 E ", " PA 12 " and " PA 12 G ".Particularly preferably be company in addition by SchaettiAG, Zurich, Switzerland is with product code

And those polyamide thermoplastics of selling of production number " 5018 ", " 5047 ", " 5045 ", " 5005 ", " 5000 ", " 5010 " and " 5065 ".Other preferred polyamide are by Degussa AG company, the Dusseldorf, Germany is with product code " Vestamelt 171 ", " Vestamelt 250 ", " Vestamelt251 ", " Vestamelt 253 ", " Vestamelt 350 ", " Vestamelt 351 ", " Vestamelt353 ", " Vestamelt 430 ", " Vestamelt 432 ", " Vestamelt 450 ", " Vestamelt451 ", " Vestamelt 470 ", " Vestamelt 471 ", " Vestamelt 640 ", " Vestamelt722 ", " Vestamelt 730 ", " Vestamelt 732 ", " Vestamelt 733 ", " Vestamelt742 ", " Vestamelt 750 ", " Vestamelt 753 ", " Vestamelt 755 ", " Vestamelt840 ", " Vestamelt X 1301 ", " Vestamelt 3041 ", " Vestamelt 3261 ", " Vestamelt X 4685 ", the polyamide thermoplastic that " Vestamelt X 7079 " and " Vestamelt X 1010 " sells.

The polyolefin that is fit among the present invention for example can obtain by the radical polymerization or the coordination polymerization of alpha-olefin, especially ethylene or propylene.Among the present invention, homopolymer and copolymer all are suitable for use as thermoplastic adhesives.If copolymer is used as thermoplastic adhesives, then in the present invention preferably these thermoplastic adhesives comprise random copolymer to small part, yet preferably mainly comprise random copolymer.In order to prepare corresponding compounds, suitable method is well known by persons skilled in the art.

Particularly preferred TPO is by Kern GmbH company, Gro β maischeid, those polyethylene and polypropylene that Germany sells with product code " PE UHMW ", " PE HMW ", " PE HMW ELS ", " PEHD ", " PE LD ", " PP-H ", " PP-C ", " PP-C HI ", " PP V2 ", " PP M20 " and " PP M40 ".Particularly preferably be company in addition by Schaetti AG, Zurich, Switzerland is with product code

And those thermoplastic polyethylenes of selling of production number " 1800 ", " 1820 ", " 1822 ", " 1825 ", " 120 " and " 140 ".

As for polyvinylesters, the polymer of vinyl acetate and copolymer are especially to be fit among the present invention.One preferred embodiment in, use the copolymer of vinyl acetate and alpha-olefin, especially ethylene.Preferably, this copolymer has that about 15-is about 40%, the vinyl acetate content of especially about 18-about 25%.This base polymer is preferably about 150-about 500 according to the melt index (MI) that ASTM D 1238 measures.

Particularly preferred thermoplastic polyethylene's base ester is by Schaetti AG company, Zurich, and Switzerland is with product code

And those polyvinylesters of selling of production number " 2047 ", " 2048 ", " 1303 " and " 2050 ".

Among the present invention, suitable polyethers for example is poly(ethylene oxide), poly(propylene oxide), polybutylene oxide or PolyTHF, especially has greater than about 5,000 molecular weight.

As for polystyrene type, the polymer of styrene or α-Jia Jibenyixi for example is fit to.

Be suitable for equally as thermoplastic adhesives with polymer be styrene-olefin block copolymers, as what can obtain by the copolymerization of styrene and monoolefine or alkadienes, particularly butadiene.About this point suitable especially be to be called as elastomeric polymer, as what can obtain by the copolymerization of styrene and butadiene or styrene and isoprene.It is same among the present invention that what be fit to is through the synthetic rubber of hydrogenant described type partially or completely.It is about 70 that the synthetic rubber that can be used as thermoplastic adhesives of the present invention among the present invention preferably has, and the number-average molecular weight of 000-about 200,000 is for example about 80, and 000-about 150,000.

The thermoplastic polymer of particularly preferred styrene-based is by Kern GmbH company, Gro β maischeid, those styrene polymers that Germany sells with product code " PS ", " PS V2 ", " SB ", " SB V0 ", " SB ELS ", " ABS ", " ABS V0 ", " ABS EMV ", " SAN ", " ASA " and " ASA HI ".

Be used for herein term " polyacrylate (polyacrylate) " or " polyacrylate (polyacrylates) ", in the content of relevant thermoplastic adhesives, the polymer or the copolymer of acrylic acid and/or its derivant had below both been referred to, again the polymer of fingernail base acrylic acid and/or its derivant or copolymer.

Can prepare polyacrylate, wherein for example ester mixture polymerization in a known way of two or more individually or as it separately of itself and simple function or polyfunctional alcohol of the derivant of acrylic acid and/or methacrylic acid and/or acrylic acid and/or methacrylic acid, for example free radical or ionic polymerization.

Among the present invention, as thermoplastic adhesives based on polyacrylate, can use homopolymer or (acrylic acid ester acrylate) also has the copolymer of styrene, acrylonitrile, vinyl acetate, propionate, vinyl chloride, vinylidene chloride, ethylene, propylene and/or butadiene in addition except acrylate.

In preparation, especially consider methacrylate, ethyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, tert-butyl acrylate, Hexyl 2-propenoate, 2-EHA or acrylic acid Lauryl Ester as monomer based on the thermoplastic adhesives of polyacrylate.Randomly, as other monomers, in polymerization process, can add a small amount of other acrylic acid, methacrylic acid, acrylamide or Methacrylamide.

Randomly, in polymerization process, can there be other acrylate with one or more functional groups and/or methacrylates.For example, these are for example 2-acrylamido-2-methyl propane sulfonic acid of maleic acid, itaconic acid, butanediol diacrylate, hexanediyl ester, triethylene glycol diacrylate, Aronix M 240, neopentylglycol diacrylate, trimethylolpropane triacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid hydroxy propyl ester, metering system acid propylene glycol ester, single-butanediol acrylate, acrylic acid glycol ester (ethyl diglycol acrylate) and the monomer that has sulfonic acid group.Particularly preferably be acrylate vinyl ester copolymer, acrylate styrol copolymer or acrylate acrylate copolymer.

Another preferred embodiment in, in powdery, water-absorbent polymers of the present invention, comprise acrylic acid and cinnamic copolymer as based on polyacrylic thermoplastic adhesives, wherein (the styrene: acrylic acid) that equals about 70: 30 of the monomer ratio in this type of hot-melt adhesive.

The thermoplastic adhesives that are contained in the powdery, water-absorbent polymers of the present invention comprise at least a above-claimed cpd.Yet thermoplastic adhesives used among the present invention also can comprise two or more described chemical compounds.

The present invention another preferred embodiment in, described thermoplastic adhesives comprise at least two kinds of polymer that are selected from leifa, vinyl acetate copolymer, poly alpha olefin, polyacrylate (polyacrylates), polymethacrylates (polymethacrylates), polyacrylate (polyacrylic acidesters), polymethacrylates (polymethacrylic acid esters), polyethers, polyester, polyamide or the polyurethane.

Except one or more above-mentioned polymer, be contained in thermoplastic adhesives in the powdery, water-absorbent polymers of the present invention and also can comprise other and make the improved additive of adhesive property.For example, so-called tackifying resin is suitable for this purpose, and it can be subdivided into natural resin and synthetic resin (artificial resin).Suitable tackifying resin for example is alkyd resins, epoxy resin, melmac, phenol resin, polyurethane resin, hydrocarbon resin and from the natural resin of Colophonium, wood turpentine and tall oil.As synthetic hydrocarbon resin, for example ketone resin, coumarone-indene resin, isocyanate resin and terpene-phenol resin are suitable.Among the present invention, preferred synthetic resin.

This resinoid can be with the amount of about 50wt% at the most, preferred 60wt% at the most and preferred especially 70wt% at the most, for example the amount (respectively based on thermoplastic adhesives) with about 35wt% of about 0.1-or the about 20wt% of about 3-is contained in the thermoplastic adhesives in the powdery, water-absorbent polymers of the present invention.

Except the composition of having mentioned, the thermoplastic adhesives that are contained in the powdery, water-absorbent polymers of the present invention can comprise at least a wax in addition.Among the present invention, " wax " is understood that to have the chemical compound that is insoluble in water of 90～about 165 ℃ of fusing points or the mixture of two or more described chemical compounds.Suitable wax for example is paraffin, Tissuemat E, polypropylene wax, montan wax, fischer-tropsch wax, microwax or Brazil wax.

In the time of in can be used for the present invention, this type of wax can be respectively be present in the thermoplastic adhesives with 60wt%, preferred 70wt% at the most and the preferred especially amount of 80wt% at the most at the most based on thermoplastic adhesives, for example with the amount of the about 60wt% of about 5-.If the chemical compound that can be obtained by the polymerization of alpha-olefin is used among the present invention as thermoplastic adhesives, the ratio of the wax in this type of hot-melt adhesive preferably amounts at least approximately 5wt% or at least approximately 10wt%.

Particularly preferably be described thermoplastic adhesives in a kind of scheme of the present invention and be applied to described powdery, water-absorbent polymers as liquid phase.For this reason, except the solution of described thermoplastic adhesives, emulsion and dispersion also are suitable.As for the solvent that is used for this liquid phase, all organic and inorganic solvents well known by persons skilled in the art all are considered to be fit to.Described liquid phase comprises described thermoplastic adhesives with the amount based on the 0.001-50wt% of quantity of solvent, preferred 0.01-25wt% and preferred especially 0.1-15wt% respectively.Particularly preferably, described liquid phase comprises the water of 60wt% at least, preferred 80wt% at least as solvent.Further preferably described liquid phase has at least a secondary cross-linking agent hereinafter described, the secondary cross-linking agent consumption of wherein preferred in this regard 0.001-20wt% and preferred especially 0.01-10wt%.

In the above-mentioned thermoplastic adhesives, sulfonated thermoplastic adhesives are particularly suitable for using in liquid phase.Wherein, sulfonated polyester, sulfonated polyamide for example nylon be particularly preferred.The another kind of thermoplastic adhesives that are suitable for liquid phase are the polyamide nylon for example of polyethoxylated, for example from the BASF AG conduct of Ludwigshafen

Available.Other are suitable in the liquid phase is that styrene acrylic copolymer is for example from SC Johnson

Comprise the ethylene vinyl acetate copolymer of the block copolymer of polyurethane and polyoxyethylene blocks, partial hydrolysis at least and comprise polyacrylate and the emulsion of polyester.

In the preferred implementation of powdery, water-absorbent polymers of the present invention, the water-absorbing polymeric particles that is contained in the described polymer is based on:

Undersaturated monomer or its salt or undersaturated monomer or its mixture that contains protonated nitrogen or quaternary nitrogen of polymeric ethylenic that contains acidic-group of polymeric ethylenic of (α 1) 0.1-99.999wt%, preferred 20-98.99wt% and preferred especially 30-98.95wt%, wherein particularly preferably be and comprise undersaturated monomer, the preferred acrylic acid mixture that contains the living group of acid of ethylenic at least

(α 2) 0-70wt%, preferred 1-60wt% and preferred especially 1-40wt% can with the polymeric ethylenically unsaturated monomers of (α 1) copolymerization,

One or more cross-linking agent of (α 3) 0.001-10wt%, preferred 0.01-7wt% and preferred especially 0.05-5wt%,

The water-soluble polymer of (α 4) 0-30wt%, preferred 1-20wt% and preferred especially 5-10wt%, and

One or more auxiliary agents of (α 5) 0-20wt%, preferred 0.01-7wt% and preferred especially 0.05-5wt%, wherein said composition weight (α 1)-(α 5) sum adds up to 100wt%.

Described single ethylenic is undersaturated contain the monomer (α 1) of acidic-group can be partly or entirely, preferred part is neutralized.The undersaturated monomer that contains acidic-group of described single ethylenic preferably is neutralized and reaches at least 25mol%, especially preferably 50mol% and even more preferably 50-90mol% at least.The neutralization of described monomer (α 1) can also can carried out after polymerization before the polymerization.In addition, neutralization can be carried out with alkali metal hydroxide, alkaline earth metal hydroxide, ammonia and carbonate and bicarbonate.In addition, all possible other alkali with described acid formation water soluble salt all are fine.Mixing neutralization with Different Alkali also is fine.Preferably with the neutralization of ammonia or alkali metal hydroxide, especially preferably with sodium hydroxide or ammonia.

In addition, free acidic-group can be occupied an leading position in polymer, to such an extent as to this polymer has the pH value in the acid range.This tart water absorbent polymer can be neutralized at least in part by the polymer (it is alkaline that this polymer is compared with described acidic polymer) that contains free basic group, preferred amino.Being called as " mixed bed ion exchange absorbable polymer " at these polymer of document (MBIEA-polymers) and has especially done open in WO99/34843.The disclosure of WO99/34843 is incorporated this paper into and by reference thus as a part of this disclosure.Usually MBIEA polymers represents compositions, and it comprises commutative anionic alkaline polymer on the one hand, comprises on the other hand with this alkaline polymer to compare the polymer that is acidity and exchangeable cations.Described alkaline polymer has basic group and its and obtains by having the monomer polymerization that basic group maybe can change into the group of basic group usually.These monomers especially have those of primary amine, secondary amine or tertiary amine or its corresponding phosphine or at least two kinds of above-mentioned functional groups.This type of monomer especially comprises the amino amylene of vinylamine (ethyleneamine), acrylic amine, diallylamine, 4-aminobutene, alkoxyl cycline (alkyloxycycline), vinyl formamide, 5-, carbodiimide (carbodiimide), formaldacin, tripolycyanamide etc., with and secondary amine or tertiary amines derived thing.

The undersaturated monomer (α 1) that contains acidic-group of preferred single ethylenic is an acrylic acid, methacrylic acid, ethylacrylic acid, α-Lv Bingxisuan, alpha-cyanoacrylate, Beta-methyl acrylic acid (.beta.-methylacrylic acid), atropic acid, β-acryloxy propionic, sorbic acid (sorbinic acid), α-chlorine sorbic acid, 2 '-methyl iso-crotonic acid, cinnamic acid, right-chloro-cinnamic acid, β-stearic acid, the itaconic acid, citraconic acid, mesaconic acid, glutaconate, aconitic acid, maleic acid, fumaric acid, three carboxyl ethylene (tricarboxythylene) and maleic anhydrides, wherein preferred especially acrylic acid and methacrylic acid and even more preferred acrylic acid.

Except these carboxy-containing acid groups' monomer, further the undersaturated monomer (α 1) that contains acidic-group of preferred single ethylenic is ethylenic unsaturated sulfonic acid monomer or the unsaturated phosphonic acids monomer of ethylenic.

Preferred ethylenic unsaturated sulfonic acid monomer is allyl sulphonic acid or aliphatic series or aromatic vinyl sulfonic acid class or acrylic compounds or methacrylic.Preferred aliphatic series or aromatic vinyl sulfonic acid class are vinyl sulfonic acid, 4-vinyl benzyl sulfonic acid, vinyl toluene sulfonic acid and styrene sulfonic acid.Preferred acrylic compounds or methacrylic are (methyl) acrylic acid sulfo group ethyl ester, (methyl) acrylic acid sulfo group propyl ester and 2-hydroxy-3-methyl acryloxy propyl sulfonic acid.As for (methyl) acrylamide alkyl sulfonic acids, preferably 2-acrylamido-2-methyl propane sulfonic acid.

The preferably unsaturated phosphonic acids monomer of ethylenic, for example the vinyl amine of vinyl phosphonate, pi-allyl phosphonic acids, vinyl benzyl phosphonic acids, (methyl) acrylamido alkyl phosphonic acid, acrylamido alkyl di 2 ethylhexyl phosphonic acid, ization and (methyl) acryloyl group phosphonate derivative in addition.

Preferably described water absorbent polymer comprises at least 50wt%, preferred 70wt% at least and the more preferably carboxy-containing acid group's of 90wt% monomer at least according to the present invention.Particularly preferably be described water absorbent polymer according to the present invention and comprise at least 50wt%, the preferred acrylic acid of 70wt% at least, it preferably is neutralized and reaches at least 20mol%, especially preferred 50mol% at least.

The ethylenically unsaturated monomers (α 1) that preferably contains protonated nitrogen is preferably (methyl) propenoic acid dialkyl aminoalkyl ester of protonated form, for example (methyl) acrylic acid dimethylamino ethyl ester hydrochlorate or (methyl) acrylic acid dimethylamino ethyl ester disulfate, and the dialkyl aminoalkyl of protonated form (methyl) acrylamide, for example dimethyl aminoethyl (methyl) acrylamide hydrochlorate, dimethylaminopropyl (methyl) acrylamide hydrochlorate, dimethylaminopropyl (methyl) acrylamide disulfate or dimethyl aminoethyl (methyl) acrylamide disulfate.

The ethylenically unsaturated monomers (α 1) that preferably contains quaternary nitrogen is (methyl) propenoic acid dialkyl ammonium Arrcostab of quaternary nitrogen form, for example (methyl) acrylic acid trimethyl ammonium ethyl ester-Methylsulfate salt or (methyl) acrylic acid dimethyl ethyl QAE quaternary aminoethyl ester-ethyl-sulfate salt, and (methyl) acrylamido alkyl dialkylamine of quaternary nitrogen form, for example (methyl) acrylamido oxypropyl trimethyl ammonium chloride, (methyl) acrylic acid trimethyl ammonium ethyl ester chloride or (methyl) acrylamido oxypropyl trimethyl ammonium sulfate.

Preferably can be acrylic amide and (methyl) acrylic amide with single ethylenically unsaturated monomers (α 2) of (α 1) copolymerization.

Possible (methyl) acrylic amide is aminoalkyl substitutive derivative for example N-methylol (methyl) acrylamide, the N of (methyl) acrylamide that replaces of alkyl or (methyl) acrylamide except acrylamide and Methacrylamide, N-dimethylamino (methyl) acrylamide, dimethyl (methyl) acrylamide or diethyl (methyl) acrylamide.Possible vinylamide class for example is N-vinylamide class, N-vinyl formamide class, N-vinyl acetamide class, N-vinyl-N-methylacetamide class, N-vinyl-N-methylformamide, vinyl pyrrolidone.Acrylamide is particularly preferred among these monomers.

In addition, as being preferably the monomer that can be scattered in the water with single ethylenically unsaturated monomers (α 2) of (α 1) copolymerization.The monomer that can be scattered in the water is preferably acrylate and methacrylate, for example (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate or (methyl) butyl acrylate and vinyl acetate, styrene and isobutene..

The preferred cross-linking agents according to the present invention (α 3) is the chemical compound (cross-linking agent type i) that has at least two ethylenic unsaturated groups in a molecule; Chemical compound (cross-linking agent Type II) with at least two functional groups that can in condensation reaction (agent of=condensation cross-linking), additive reaction or ring-opening reaction, react with the functional group of monomer (α 1) or (α 2); Chemical compound (cross-linking agent type-iii) with functional group that at least one ethylenic unsaturated group and at least one can react in condensation reaction, additive reaction or ring-opening reaction with the functional group of monomer (α 1) or (α 2); Perhaps multivalent metal cation (cross-linking agent type i V).Thus for the chemical compound of cross-linking agent type i, the crosslinked of described polymer realized by the ethylenic unsaturated group of described cross-linker molecules and the radical polymerization of described single ethylenically unsaturated monomers (α 1) or (α 2), and for the multivalent metal cation of the chemical compound of cross-linking agent Type II and cross-linking agent type i V, the crosslinked condensation reaction by described functional group (cross-linking agent Type II) and described monomer (α 1) or (α 2) functional group respectively of described polymer or the electrostatic interaction by described multivalent metal cation (cross-linking agent type i V) and described monomer (α 1) or (α 2) functional group realize.For the chemical compound of cross-linking agent type-iii, described polymer crosslinked correspondingly by the radical polymerization of described ethylenic unsaturated group or in addition the condensation reaction between the functional group of the functional group by described cross-linking agent and described monomer (α 1) or (α 2) realize.

The preferred compound of cross-linking agent type i is poly-(methyl) acrylate, it is for example by making polyhydric alcohol such as ethylene glycol, propylene glycol, trimethylolpropane, 1,6-hexanediol, glycerol, tetramethylolmethane, Polyethylene Glycol or polypropylene glycol with acrylic or methacrylic acid; Amino alcohol, polyalkylene polyamine such as diethylenetriamines or trien; Or oxyalkylated polyhydric alcohol transforms and obtains.The preferred chemical compound of other of cross-linking agent type i is (methyl) acrylate of polyvinyl compound, poly-(methyl) allyl compound, mono-vinyl chemical compound or (methyl) acrylate of single (methyl) allyl compound, is preferably list (methyl) allyl compound of polyhydric alcohol or amino alcohol.Can be about this point with reference to DE 19,543 366 and DE 195 43 368.Its disclosure is incorporated this paper by reference into and is considered to a part of this disclosure.

Cross-linking agent type i examples for compounds is two (methyl) acrylic acid alkenyl esters, two (methyl) acrylic acid glycol ester for example, two (methyl) acrylic acid 1, the ammediol ester, two (methyl) acrylic acid 1, the 4-butanediol ester, two (methyl) acrylic acid 1, the 3-butanediol ester, two (methyl) acrylic acid 1,6-hexanediol ester, two (methyl) acrylic acid 1,10-decanediol ester, two (methyl) acrylic acid 1,12-dodecanediol ester, two (methyl) acrylic acid 1,18-octacosanol ester, two (methyl) acrylic acid ring pentadiol ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid methylene ester or tetramethylolmethane two (methyl) acrylate; Thiazolinyl two (methyl) acrylamide, for example N-methyl two (methyl) acrylamide, N, two (methyl) acrylamides of N '-3-methyl butylidene, N, N '-(1,2-dihydroxy ethylidene) two (methyl) acrylamide, N, two (methyl) acrylamides of N '-hexylidene or N, N '-di-2-ethylhexylphosphine oxide (methyl) acrylamide; Poly alkoxyl two (methyl) acrylate, diethylene glycol two (methyl) acrylate for example, 2,2'-ethylenedioxybis(ethanol). two (methyl) acrylate, tetraethylene glycol (TEG) two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate or four propylene glycol two (methyl) acrylate, bisphenol-A-two (methyl) acrylate, ethoxylation bisphenol-A-two (methyl) acrylate, two (methyl) acrylic acid benzylidene ester, 1,3-two (methyl) acryloxy the third-2 alcohol, hydroquinone two (methyl) acrylate, (it is preferably with every hydroxyl 1-30mol alkylene oxide alkoxylate for two (methyl) acrylate of trimethylolpropane, preferred ethoxylation), THIOGLYCOL two (methyl) acrylate, sulfo-propylene glycol two (methyl) acrylate, sulfo-Polyethylene Glycol two (methyl) acrylate, sulfo-polypropylene glycol two (methyl) acrylate; Divinyl ether, for example 1,4-butanediol divinyl ether; Divinyl ester, for example divinyl adipate ester; Dienes, butadiene or 1 for example, 6-hexadiene, divinylbenzene; Two (methyl) allyl compound, for example homopolymer and the copolymer of the homopolymer of two (methyl) pi-allyl phthalic acid ester or two (methyl) pi-allyl succinate, two (methyl) allyl dimethyl ammonium chloride and copolymer and diethyl (methyl) allyl amino methyl (methyl) acrylate ammonium chloride; Vinyl (methyl) acyclic compound, for example (methyl) acrylic acid vinyl esters; (methyl) pi-allyl (methyl) acyclic compound, for example (methyl) acrylic acid (methyl) allyl ester, with (methyl) acrylic acid (methyl) allyl ester of every hydroxyl 1-30mol oxirane ethoxylation; Two (methyl) allyl ester of polybasic carboxylic acid, for example maleic acid two (methyl) allyl ester, fumaric acid two (methyl) allyl ester, succinic acid two (methyl) allyl ester or p-phthalic acid two (methyl) allyl ester; Have 3 or the chemical compound of the group of the undersaturated free redical polymerization of multi-ethylenical more, glycerol three (methyl) acrylate for example, preferably with (methyl) acrylate of the glycerol of every hydroxyl 1-30mol oxirane ethoxylation, trimethylolpropane tris (methyl) acrylate, preferably with every hydroxyl 1-30mol alkylene oxide alkoxylate, trimethylolpropane tris (methyl) acrylate of preferred ethoxylation, the trimethyl acrylamide, inferior (methyl) pi-allyl two (methyl) acrylate, 3-allyloxy-1,2-propylene glycol two (methyl) acrylate, three (methyl) pi-allyl cyanurate, three (methyl) pi-allyl isocyanuric acid ester, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, preferably with (methyl) acrylate of the tetramethylolmethane of every hydroxyl 1-30mol oxirane ethoxylation, three (2-hydroxyethyl) isocyanuric acid ester three (methyl) acrylate, the trivinyl trimellitate, three (methyl) allyl amine; Two (methyl) pi-allyl alkylamine, for example two (methyl) pi-allyl methylamine; Three (methyl) pi-allyl phosphate ester, four (methyl) pi-allyl ethylenediamine, poly-(methyl) allyl ester, four (methyl) allyloxy ethane or four (methyl) pi-allyl halogenation ammonium.

The chemical compound of cross-linking agent Type II for preferably have at least two can with the functional group of described monomer (α 1) or (α 2), the preferably chemical compound of the functional group of in condensation reaction (agent of=condensation cross-linking), additive reaction or ring-opening reaction, reacting with the acidic-group of described monomer (α 1).These functional groups of cross-linking agent Type II chemical compound are preferably alcohol, amine, aldehyde, (+)-2,3-Epoxy-1-propanol (glycidic), isocyanates, carbonic ester or chloropropylene oxide official energy.

Can mention polyhydric alcohol as cross-linking agent Type II examples for compounds, ethylene glycol for example, poly ethylene glycol such as diethylene glycol, 2,2'-ethylenedioxybis(ethanol). and tetraethylene glycol (TEG), propylene glycol, poly propylene glycol such as dipropylene glycol, tripropylene glycol or four propylene glycol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 2, the 4-pentanediol, 1, the 6-hexanediol, 2, the 5-hexanediol, glycerol, polyglycereol, trimethylolpropane, polypropylene oxide, ethylene oxide-oxypropylene block copolymer, sorbitan-fatty acid ester, polyethylene glycol oxide sorbitan-fatty acid ester, tetramethylolmethane, polyvinyl alcohol and Sorbitol; Amino alcohol, for example ethanolamine, diethanolamine, triethanolamine or Propanolamine; Polyamine chemical compound, for example ethylenediamine, diethylenetriamines, trien, tetren or penten; Poly glycidyl ether compound such as Ethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, glycerol diglycidyl ether, glycerol poly glycidyl ether, tetramethylolmethane poly glycidyl ether, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, hexanediol glycidyl ether, trimethylolpropane poly glycidyl ether, Sorbitol poly glycidyl ether, o-phthalic acid diglycidyl ester, adipic acid diglycidyl ether, 1,4-phenylene two (2-oxazoline), (+)-2,3-Epoxy-1-propanols; Poly isocyanate, preferred vulcabond is 2,4 toluene diisocyanate and hexamethylene vulcabond for example; Polyaziridine chemical compound for example 2, the two methylol butanols-three [3-(1-aziridinyl) propionic ester] of 2-, hexamethylene diethylidene urea and diphenyl methane-two-4,4 '-N, N '-diethylidene urea; Halogenated epoxide is chloropropylene oxide, epibromohydrin and Alpha-Methyl chloropropylene oxide for example; Alkylene carbonates for example 1,3-dioxolanes-2-ketone (ethylene carbonate), 4-methyl isophthalic acid, 3-dioxolanes-2-ketone (propylene carbonate), 4,5-dimethyl-1,3-dioxolanes-2-ketone, 4,4-dimethyl-1,3-dioxolanes-2-ketone, 4-ethyl-1,3-dioxolanes-2-ketone, 4-methylol-1,3-dioxolanes-2-ketone, 1,3-diox-2-ketone, 4-methyl isophthalic acid, 3-diox-2-ketone, 4,6-dimethyl-1,3-diox-2-ketone, 1,3-dioxolanes-2-ketone, poly--1,3-dioxolanes-2-ketone; The polybrene class is the condensation product of dimethylamine and chloropropylene oxide for example.Other preferred compounds of described in addition cross-linking agent Type II are for example ethylene bisoxazoline of Duo Ju oxazoline; Cross-linking agent with silane group is γ-glycidoxypropyltrime,hoxysilane and gamma-amino propyl trimethoxy silicane for example; The oxazolidine ketone is 2-oxazolidone, two-and poly-2-oxazolidone for example; And silicic acid diethylene glycol ester.

The preferred compound of type-iii contains hydroxyl or amino ester for (methyl) is acrylic acid, for example (methyl) acrylic acid 2-hydroxyethyl ester, and (methyl) acrylamide that contains hydroxyl or amino, or the list of glycol (methyl) allyl compound.

The multivalent metal cation of described cross-linking agent type i V preferably is derived from the cation that has single electric charge or multi-charge, has unicharged especially from alkali metal for example potassium, sodium, lithium, wherein preferred lithium.Preferably have doubly charged cationic source from zinc, beryllium, alkaline-earth metal for example magnesium, calcium, strontium, wherein preferably magnesium.Be suitable for other cationes with higher electric charge of the present invention and be cation from the mixture of aluminum, ferrum, chromium, manganese, titanium, zirconium and other transition metal and these cationic double salt or described salt.Preferred aluminum salt and vitriol and multiple hydrate, for example AlCl of using ₃6H ₂O, NaAl (SO ₄) ₂12H ₂O, KAl (SO ₄) ₂12H ₂O or Al ₂(SO ₄) ₃14-18H ₂O.

Especially preferably use Al ₂(SO ₄) ₃And hydrate is as the cross-linking agent of described cross-linking agent type i V.

Preferred water absorbent polymer is cross-linking agent by following cross-linking agent type or the cross-linking agent by following cross-linking agent type combination respectively: I, II, III, IV, I II, I III, I IV, I II III, I II IV, I III IV, II III IV, II IV or III IV and crosslinked those.The preferred implementation of the cross-linking agent of water-absorbing polymeric particles is represented in the combination of above-mentioned cross-linking agent type respectively.

Other preferred implementations of described polymer are the crosslinked polymer of any above-mentioned cross-linking agent by the cross-linking agent type i.Wherein preferred water-soluble cross-linker.About this point, N, N '-methylene-bisacrylamide, Polyethylene Glycol two (methyl) acrylate, triallyl ammonio methacrylate, tetra allyl ammonium chloride and to use pi-allyl glycol in the ninth of the ten Heavenly Stems acrylate that makes with respect to the acrylic acid 9mol oxirane of every mol be particularly preferred.

As for water-soluble polymer (α 4), the for example part or all of saponified polyvinyl alcohol of water-soluble polymer, polyvinyl pyrrolidone, starch or starch derivatives, Polyethylene Glycol or polyacrylic can be contained in the described water-absorbing polymeric particles, and preferably polymerization enters described water-absorbing polymeric particles.The molecular weight of these polymer is also non-key, as long as it is water miscible.Preferred water-soluble polymer is starch or starch derivatives or polyvinyl alcohol.Described water-soluble polymer, preferred synthetic polymer such as polyvinyl alcohol also can be used as the grafting matrix for the treatment of polymerization single polymerization monomer.

As for additive (α 5), suspending agent, abnormal smells from the patient bonding agent, surfactant or antioxidant preferably are contained in the described water-absorbing polymeric particles.

The above-mentioned polymer beads that is contained in the powdery, water-absorbent polymers of the present invention preferably prepares by the preferred polymerisation in bulk of carrying out in mediating reactor such as extruder or by belt polymerization (beltpolymerisation), polymerisation in solution, injection polymerization (spray polymerisation), inverse emulsion polymerization and inverse suspension polymerization.Polymerisation in solution is preferably carried out in as the water of solvent.Described polymerisation in solution can be carried out continuously or off and on.Described polymerisation in solution is carried out preferably as the belt polymerization (band polymerization) of operation continuously.For example the type of temperature, initiator and consumption and reaction path can be recognized from prior art widely and may change scheme about reactive moieties.Typical technology is described in following patent specification: US 4,286,082, DE 27 06135, US 4,076,663, DE 35 03 458, DE 40 20 780, DE 42 44 548, DE 43 23001, DE43 33 056, DE 44 18 818.Its disclosure is incorporated this paper by reference into and is formed a part of this disclosure thus.

For will transform into mean diameter at least 100 μ m by the water absorbent polymer that above-mentioned polymerization obtains, preferably less than 150 μ m and especially preferably less than the particle form of 200 μ m, at its after separating from reactant mixture, these polymer can be at first at 20-300 ℃, preferred 50-250 ℃ and be dried under preferred 100-200 ℃ the temperature especially respectively in the gross weight of described polymer less than 40wt%, preferably less than 20wt% and even be more preferably less than the water content of 10wt%.Described drying is preferably carried out in baking oven or exsiccator well known by persons skilled in the art, for example in belt dryer, dry hedge (" Hordentrockner "), rotary kiln, fluidized bed dryer, pan dryer, pedal-type dryer or infrared drier.If the polymer of the drying that obtains thus still is not to exist with particle form, it must further be pulverized after drying so.Pulverize and preferably undertaken, preferably by in hammer mill, needle mill, ball mill or roll mill, dry grinding by dry grinding.

Except above-mentioned being used for becomes described polymer transition the method for particle form, polymer also can be pulverized with gel state by adopting any wet grinding to carry out wet-grinding technology and relative device with conventional equipment.

Another preferred embodiment in, be contained in described water-absorbing polymeric particles in the described powdery, water-absorbent polymers and be based on Biodegradable material.Natural polysaccharide belongs to this type of material, and it has comprised carboxyl or natively by having carboxyl with post-modification.First kind polysaccharide can comprise for example starch, amylose, amylopectin, cellulose and polygalactomannan such as guar gum and locust bean gum, and second apoplexy due to endogenous wind can comprise for example xanthan gum, alginate, Radix Acaciae senegalis.

Another preferred embodiment in, be contained in described water-absorbing polymeric particles in the described powdery, water-absorbent polymers based on the mixture of biodegradable and synthetic water-absorbing polymeric particles.

According to the present invention further preferably, described water-absorbing polymeric particles has interior section, centers on the exterior section of this interior section and the surface portion that centers on described exterior section, wherein said exterior section has the degree of cross linking higher than its interior section, to such an extent as to preferably form nucleocapsid structure.The crosslinked action that increases in the surface portion of the described powdery, water-absorbent polymers preferably secondary cross-linking of the reactive group by near surface realizes.This secondary cross-linking can be heat cross-linking, photochemical crosslinking or chemical crosslinking.As for the secondary cross-linking agent that chemical secondary cross-linking is used, the chemical compound of mentioning as the cross-linking agent (α 3) of cross-linking agent Type II and IV is preferred.Especially preferably agent is an ethylene carbonate as secondary cross-linking.

Be used for preparing the method for powdery, water-absorbent polymers in the present invention, preferred as composition:

-0.01-20wt%, preferred 0.1-15wt% and even the more preferably fine particle that preferably is not based on water-absorbent crosslinked poly-(methyl) acrylate of 1-10wt%, it is less than 200 μ m, preferably less than 100 μ m and especially preferably less than the mean diameter that screen analysis is measured of passing through of 50 μ m;

The thermoplastic adhesives of-0.001-10wt%, preferred 0.01-5wt% and preferred especially 0.5-1wt%;

The water-absorbing polymeric particles of the mean diameter of passing through screen analysis mensuration of-60-99.998wt%, preferred 70-99wt% and preferred especially 90-95wt% with at least 200 μ m, preferred at least 250 μ m and preferred especially at least 300 μ m, wherein mentioned component adds up 100wt%

-at 120-250 ℃, preferred 150-220 ℃ and make their contacts especially under preferred 170-200 ℃ the temperature.

In a kind of scheme of said method, use at least a above-mentioned secondary cross-linking agent in addition as other compositions.Preferred in this case described water absorption fine particle is not by secondary cross-linking or correspondingly surface-crosslinked.In this scheme further preferably thermoplastic adhesives and secondary cross-linking agent in liquid phase, preferably in aqueous solution, use, wherein above in part about liquid phase given concentration also be preferred herein.Preferably make the secondary cross-linking agent contact about this point as other composition.Particularly preferably be herein described secondary cross-linking agent and thermoplastic adhesives are added in described other compositions together, wherein described at least secondary cross-linking agent can be present in the liquid phase.

As for water-absorbing polymeric particles, thermoplastic adhesives and fine particle, those water-absorbing polymeric particles, thermoplastic adhesives or the fine particle of having mentioned in the part about powdery, water-absorbent polymers of the present invention is preferred.

Preferably described thermoplastic adhesives are with particulate form, preferably use with powder or fine-grained form according to the present invention, wherein at least the described powder of 50wt%, preferred 70wt% at least or particulate have 1-200 μ m, especially preferred 10-150 μ m and even more preferably 20-120 μ m pass through the particle diameter that screen analysis is measured.

If the thermoplastic adhesives of mentioning in the part of powdery, water-absorbent polymers of the present invention are not to exist with particulate form in its production or after carrying, if especially for example it exists with bulk form, these can transform by breaking method well known by persons skilled in the art, for example by grinding or by extruding via disintegrating machine plate (breaker plate) and then the granule of being extruded being ground into the particulate form with essential mean diameter.Randomly, can use special Ginding process, for example at low temperatures, cryogrinding under the temperature of fusing point that is lower than used thermoplastic adhesives or glass transition temperature especially.Be the brittleness of described hot-melt adhesive for an important requirement that is ground to required particle diameter.

Combining of described water-absorbing polymeric particles, thermoplastic adhesives and fine particle can be carried out by any way.Yet, a requirement of production powdery, water-absorbent polymers of the present invention is to satisfy the certain at least time of contact between water-absorbing polymeric particles, thermoplastic adhesives and the fine particle, its feasible cementation that described thermoplastic adhesives are facilitated of passing through that is implemented between at least one water-absorbing polymeric particles and at least one fine particle.Preferably, to such an extent as to measure and form this as far as possible little aggregation time of contact, it only comprises a water-absorbing polymeric particles ideally separately and one or morely is applied to the lip-deep fine particle of this water-absorbing polymeric particles by means of thermoplastic adhesives.What preferably should avoid is to be caused by long time of contact forming the aggregation that comprises some water-absorbing polymeric particles by the cementation of thermoplastic adhesives.

Combining of described water-absorbing polymeric particles, thermoplastic adhesives and fine particle can be undertaken by any way according to the inventive method.Thereby for example the thermoplastic adhesives of described particulate form and described fine particle can begin to contact with described water-absorbing polymeric particles in the preparation process of described water-absorbing polymeric particles.For this purpose, for example suitable is, in the secondary cross-linking process of described water-absorbing polymeric particles this water-absorbing polymeric particles to be contacted with described fine particle with the thermoplastic adhesives granule carrying out in producing superabsorbents as common.

As for the order of single composition contact, can carry out by different way.

In an embodiment of the inventive method, at first described water-absorbing polymeric particles is mixed with the particulate thermoplastic binding agent of solid state.The water-absorbing polymeric particles that contacts with thermoplastic adhesives can mix with described fine particle then in this way.For the adhesion of the described fine particle realizing facilitating to this water absorbent polymer particulate surface by described thermoplastic adhesives, these thermoplastic adhesives must at first heat by elevated temperature to fusion temperature or the temperature more than the glass transition temperature, so that it has adhesive performance.This heating can proceed to that described water-absorbing polymeric particles has contacted with described thermoplastic adhesives but time of not contacting with described fine particle as yet.In this case, the mixture of described polymer fine particles and thermoplastic adhesives correspondingly is heated to the above temperature of fusion temperature of thermoplastic adhesives, and makes this mixture contact with described fine particle subsequently.In order to prevent the undesirable gathering of described water-absorbing polymeric particles, polymer beads that maybe advantageously will contact with described binding agent is cooled to the temperature below the fusion temperature of these thermoplastic adhesives temporarily.In this cooling stage, should make described water-absorbing polymeric particles motion.This type games can for example cause by stir, vibrate or mobile etc.When the water-absorbing polymeric particles that applies with thermoplastic adhesives with after described fine particle contacts, elevated temperature is to the fusion temperature of thermoplastic adhesives or the temperature more than the glass transition temperature once more, so that guarantee the adhesion between described water-absorbing polymeric particles and the fine particle.In addition, in the another kind of scheme of the inventive method, described water-absorbing polymeric particles can at first mix with described fine particle and can add described thermoplastic adhesives then, and then heating is to melt this thermoplastic adhesives.Can obtain the more uniform mixture of described fine particle and described water-absorbing polymeric particles by this way, it causes less dust to form and improved flowability.

Yet, also can heat described thermoplastic adhesives to its time that contacts with described water-absorbing polymeric particles not yet.In this case, at first described thermoplastic adhesives are heated to its fusion temperature or the temperature more than the glass transition temperature, then it are begun to contact with described water-absorbing polymeric particles.Its water-absorbing polymeric particles that contacts with described thermoplastic adhesives will be mixed with described fine particle, wherein also can cool off herein temporarily to prevent the formation of big aggregation.

In another embodiment of the inventive method; its as indicated above carrying out; different is at first described fine particle to be mixed with the described microgranule thermoplastic adhesives of solid form, and the described fine particle that will contact with thermoplastic adhesives mixes with described water-absorbing polymeric particles then.

Yet in another particularly preferred embodiment of the inventive method, described fine particle, water-absorbing polymeric particles and thermoplastic adhesives are contacted simultaneously.Thereby, the thermoplastic adhesives of described particulate form can the temperature below fusion temperature mix with described water-absorbing polymeric particles and described fine particle, the mixture heated that will so obtain is to the above temperature of the fusion temperature of described thermoplastic adhesives then, so that guarantee the adhesion that causes by described thermoplastic adhesives between described fine particle and water-absorbing polymeric particles.Also can at first heat described thermoplastic adhesives to its temperature more than fusion temperature and the thermoplastic adhesives that will so heat and described fine particle and water-absorbing polymeric particles is mixed together.In this embodiment of the inventive method, in order to prevent the undesirable gathering of described water-absorbing polymeric particles, also the polymer beads that contacts with described binding agent temporarily can be cooled to the fusion temperature of these thermoplastic adhesives or the temperature below the glass transition temperature.In this cooling stage, should make described water-absorbing polymeric particles motion.

Described water-absorbing polymeric particles can carry out in mixing apparatus well known by persons skilled in the art with contacting of described thermoplastic adhesives and fine particle.The mixing apparatus that is fit to for example be Patterson-Kelley blender, DRAIS turbulent flow blender,

Blender, Ruberg blender, ribbon mixer, board-like blender and fluidized bed for solid mixing and continuous service, preferred vertical holding furnace, wherein said granule mix by means of swivel knife with fast frequency and have a conveyer device that is movably heated.

According to the present invention preferably, if further making described powdery, water-absorbent polymers at the surface portion secondary cross-linking in the treatment step, wherein those secondary cross-linking agent that have been mentioned as preferred secondary cross-linking agent in powdery, water-absorbent polymers part of the present invention are preferred.

Exist the multiple probability of secondary cross-linking selection of time in the method for the present invention.

In an embodiment of the inventive method, described secondary cross-linking described water-absorbing polymeric particles and described thermoplastic adhesives with take place before described fine particle contacts.In this case, with described secondary cross-linking agent, preferably contact with comprising the fluid of solvent with the secondary cross-linking agent, described solvent preferred water, organic solvent such as methanol, ethanol, 1-propanol or 2-propanol or its be both mixture at least with described polymer fine particle.Described water-absorbing polymeric particles that then will contact with described secondary cross-linking agent is heated to 50-300 ℃, preferred 100-250 ℃ and especially preferred 150-200 ℃ temperature, so that carry out secondary cross-linking.Polymer beads with secondary cross-linking like this contacts with fine particle with thermoplastic adhesives as mentioned above subsequently.

In another embodiment of the inventive method, described secondary cross-linking described water-absorbing polymeric particles and described thermoplastic adhesives with carry out after described fine particle contacts.In this case, fine particle is able to secondary cross-linking by means of the fixed powdery, water-absorbent polymers of thermoplastic adhesives with type mentioned above and method in its surface portion.

In preferred implementation of the inventive method, described secondary cross-linking carries out in the contact process of described water-absorbing polymeric particles and described thermoplastic adhesives and described fine particle.Particularly preferably be herein, described water-absorbing polymeric particles and described preferred particulate thermoplastic adhesives, described fine particle and described secondary cross-linking agent the secondary cross-linking agent of the fluid form that comprises this secondary cross-linking agent and solvent (preferably with) mix, and are heated to the above temperature of fusion temperature then.

Preferably, the consumption of described secondary cross-linking agent be 0.01-5wt%, especially be preferably 0.3-3wt% and even 0.5-1.5wt% more preferably, respectively based on the weight of described water-absorbing polymeric particles.If described secondary cross-linking agent is with fluid form, preferably use with the form of aqueous solution or aqueous dispersion, so described fluid preferably with 10-80wt%, preferred especially 30-70wt% and even more preferably the amount of 40-50wt% comprise the secondary cross-linking agent, respectively based on this fluidic gross weight.

The invention still further relates to by the available powdery, water-absorbent polymers of said method, wherein these powdery, water-absorbent polymers preferably have and the identical performance of foregoing powdery, water-absorbent polymers of the present invention.

Particularly preferably, be characterised in that by the available powdery, water-absorbent polymers of the inventive method:

P1 1-13, preferred 3-9, preferred especially 4-8 and even the more preferably flow valuve of 5-7 (FFC); Or

P2 at the most 6, preferred at the most 4, preferred especially 2 dust ratio at the most.

The powdery, water-absorbent polymers further preferably of the present invention and have at least a, preferred all following performances in the following performance according to the present invention by the available powdery, water-absorbent polymers of the inventive method:

Abrasion index (the Ai of P3 1-17, preferred 1.1-15 and preferred especially 1.5-10;

The wearing and tearing difference A of P4 0-7, preferred 1.1-6 and preferred especially 1.5-3 _d

P5 is 20g/g, preferred 25g/g at least, preferred especially 27g/g at least and even the more preferably reserve capability of measuring according to ERT441.1-99 of 27-35g/g at least.

Preferred implementation of the present invention is represented in the performance combination that comes from two or more these performances of above-mentioned performance P1-P5 respectively.Further preferably, powdery, water-absorbent polymers granule of the present invention has following with letter or described performance of monogram or performance combination: P1P3P4P5, P1P5, P1P3P5, P3P5 or P1P2P3P4P5.

In one embodiment, the present invention relates to a kind of powdery, water-absorbent polymers, its crosslinked, part neutralization and preferred neutralization that comprises 30wt% at least, preferred 75wt% at least and preferred especially 95wt% at least reaches the polyacrylic acid of 60-80mol%, and have among the performance P1-P5 at least a, preferred all, preferred properties combination P1P3P4P5, P1P5, P1P3P5 and even more preferably performance combination P3P5.

In addition preferably, at least 50wt%, preferred especially 70wt% at least and even more preferably at least 90wt% pass through the available powdery, water-absorbent polymers of the inventive method and powdery, water-absorbent polymers of the present invention has greater than 50 to 2,000 μ m, preferred 100-1,500 μ m and even more preferably 200-1,200 μ m pass through the particle diameter that screen analysis is measured.

In transmission method of the present invention, by available powdery, water-absorbent polymers of the inventive method or the powdery, water-absorbent polymers of the present invention pipeline of flowing through, wherein this pipeline preferably constitutes the part of the metering system of the part of the equipment of producing water absorbent polymer or water absorbent polymer.This type of metering system for example can be used in charge cask or the charging bag or is arranged in air lay or rhombus weavy grain machine (Windelmaschinen).Particularly preferably, described pipeline be wherein when with they with fibrous material as cotton fiber contact transmit when forming absorbent cores respectively or absorbing nuclear (" Kern ") as described in the pipeline of powdery, water-absorbent polymers.

Complex of the present invention comprises above-mentioned powdery, water-absorbent polymers and matrix.Preferably, powdery, water-absorbent polymers of the present invention and described matrix are fixed together.As for matrix, the layer of for example being made from polyethylene, polypropylene or polyamide by polymer, metal, non-woven material, fine hair, fabric, net, natural or synthetic fibers or other foams are preferred.

As for complex, preferably encapsulant, cable, absorbent cores and diaper and comprise these hygienic articles according to the present invention.

In the method for preparing complex of the present invention, be in contact with one another with powdery, water-absorbent polymers of the present invention or by the available powdery, water-absorbent polymers of the inventive method and matrix and non-essential suitable auxiliary agents.Described contact preferably by wet-laying and air-laid process, suppress, extrude and mixing is carried out.

The invention still further relates to by the available complex of said method.

The invention further relates to chemicals; especially the carrier used of foam, molded body, fiber, tablet, film, cable, encapsulant, Liquid Absorption hygienic articles, plant or conk regulator or plant protecting activity material, construction material be with additive, packaging material or soil additive, and it comprises powdery, water-absorbent polymers of the present invention or by available powdery, water-absorbent polymers of the inventive method or above-mentioned complex.The feature of described chemicals especially is special excellent biodegradability.

In addition, the present invention relates to powdery, water-absorbent polymers of the present invention or by the available powdery, water-absorbent polymers of the inventive method or above-mentioned complex at hygienic articles, resist flood, isolated water, the control of the adjusting soil water or handle purposes in the food.

At last, the invention still further relates to thermoplastic adhesives and for the powdery, water-absorbent polymers that does not comprise these thermoplastic adhesives, changing the flow valuve (FFC) of the powdery, water-absorbent polymers that comprises these thermoplastic adhesives or the purposes in the dust ratio, wherein as thermoplastic adhesives, preferred those that mentioned in powdery, water-absorbent binding agent part of the present invention.

Now the present invention is described in more detail by method of testing and non-limiting example.

Method of testing

The mensuration of FFC value

The FFC value provides the information about the mobile performance of discrete material in feed bin.In this test, discrete material stands different stress.Flow behavior can followingly characterize:

Do not flow in FFC＜1

Adhere in 1＜FFC＜2 very much

2＜FFC＜4 adhesions

Slightly flow in 4＜FFC＜10

10＜FFC free-flow

If discrete material is flowed,, there is good flow behavior from funnel or feed bin if for example discrete material need not compacting and just flows out.Interruption or its compacting between conveying or storage life can take place to flow out in the discrete material for the flowability difference.Term " flows " and refers to discrete material owing to stress and with plasticity mode generation deformation.

Relevant mensuration FFC tests the more details of executing mode really conscientiously can be at the Dr.Ing.DitmarSchulze paper in February, 2002 " Das automatische

RST-01.pc " and " Fliesseigenschaften von Sch ü ttg ü tern undverfahrenstechnische Siloauslegung " in 2002 in find.In this test, use the artificial modification of circular shearing equipment RST-01.01.

The mensuration of dust ratio

Dust ratio Palas company, Germany, " Dust View " type measuring apparatus.For this reason, the sample with 30.00g is placed in the funnel tube.When beginning test, hopper gate is opened automatically and sample falls into the dust bin.Form the minimizing (minimizing of transmission) of Laser Measurement bundle by dust.This value is used for the measurement that the dust ratio is a turbidity, represents with the percentage ratio of 1-100 scale.The dust value that initial value when the dust ratio begins by measuring and the floating part of measurement recorded after 30 seconds provides.Thereby draw the dust ratio by initial value and dust value sum.

The mensuration of abrasion index and wearing and tearing difference

Use the assay device shown in Fig. 1 for this reason.It comprises the funnel 1 of sample being introduced detecting chamber 2.Between funnel and detection absorption chamber 2, provide the conduit that has charging valve V1 and have the feeding line of the gas control valve V2 that is arranged on charging valve V1 below.By V2, sample absorption chamber 2 is applied the pressure of 4.3bar.Its cylinder by diameter 9cm and long 16cm constitutes.Blunt nosed conical lower part is connected on this cylinder, and described lower part has the lower openings of diameter 4cm.Connected is the pipe of the long diameter 4cm of 2cm, and it leads to another blunt nosed conical portion of length 4.5cm and lower diameter 1.75cm again.Connected is chamber outlet valve V3.Since V3, the pipeline of internal diameter 10mm and total length 1101cm extends by 90 degree and the long sweep of 4.5cm.This pipeline begins with the straight portions of 30cm, then is 16 straight portions of the long 60cm separately that is connected with 90 degree and the long sweep of 4.5cm, and these 16 straight portions are spent bending sections and linked together by being respectively 180 of 4.5cm.What link to each other by the long crooked joint of 90 degree and 4.5cm with these 16 straight portions is another linear parts that 30cm grows.This section is led in the sample collection chamber 4, and 2 different parts only are in textural and chamber for it, adopts to have the filter bag of comparing much smaller aperture with the particle diameter of sample and replace described loam cake.The sample collection chamber removes valve V4 sealing in the bottom by sample.All metal parts of above-mentioned assay device are made by 316 stainless steel alloys.Pipe is the standard memotron.The inner surface of this device single component is slick.Use is from Milwaukee Valve Company, the 20 SS0R-02-LL-9102 type valves of USA.

The following operation of said apparatus:

The charging of step 1-sample

Open valve V1, V4, valve-off V2 and V3.With funnel 1 the 50g sample is packed in the chamber 2.

The transmission of step 2-sample

Valve starts according to following order: a) V1 closes, and b) V2 opens, and c) V3 closes.Pipeline no longer show by sample by the vibration that causes after, following valve location is set: a) V2 closes, V1 opens, V3 closes.

Step 3-sample shifts out

For shifting out sample, under V4, place container, by careful unlatching V4 sample is packed in this container with further detection.And then close V4.

In order to measure (S before the wearing and tearing _VorA) and (S afterwards _NachA) the dust ratio, sample is measured before step 1 He after the step 3 according to DIN55992-2.

" abrasion index " A _iBy A _i=S _AfterA/ S _BeforeADraw.

" wearing and tearing difference " A _dBy A _d=S _AfterA-S _BeforeADraw.

Embodiment

In the following example, granulous, lightly crosslinked, the neutral polyacrylic acid of part is used as pre-product, and it can be from Stockhausen GmbH ﹠amp; Co.KG is with trade name

Model Z3050 buy.It has the reserve capability of 33g/g and 3.7 dust ratio.

Embodiment 1

The preparation of powdery, water-absorbent polymers of the present invention:

Be placed on the fine particle of listed amount in 1000g pre-product and the table 1 and thermoplastic adhesives in the vertical blender (MTI-Mischtechnik Industrieanlagen GmbH, model LM1.5/5) and under 750rpm, merge with 40g 25wt% ethylene carbonate solution.

Coated pre-product is transferred to Gericke powder conveyer (Gericke GmbH, model GLD75) is sent to continuously in the Labor-Nara-reactor (HTM Reetz GmbH, model is laboratory arm mixer " Mini-Nara II ") in and with the conveyer performance of 20g/min.The time of staying in exsiccator is about 90 minutes and product is heated to 185-195 ℃ maximum temperature.During this period, the fusing of secondary cross-linking and described thermoplastic adhesives taking place, influence flow behavior, will self be distributed in upward surperficial and make described fine particle be bonded on the surface of water-absorbing polymeric particles.

Table 1

¹⁾The product of Schaetti AG company, Zurich, Switzerland; Melting range: 130-160 ℃, the melt viscosity under 160 ℃: 520Pas, heat stability: 120 ℃.

Embodiment 2

The result who compiles in the table 2 is that the 25wt% ethylene carbonate solution with the material of listing in the table 2 and consumption and 60g prepares as described in example 1 above.Described sample is carried out wear test.After carrying out wear test, measure the FFC value.Before carrying out wear test and measure crc value afterwards.

Table 2

²⁾The product of Degussa AG, Dusseldorf, Germany

³⁾Measure for four times

Embodiment 3

In the presence of the superabsorbents fine particle, prepare powdery, water-absorbent polymers by applying with thermoplastic adhesives;

Be placed on the thermoplastic adhesives of listed amount in 1000g pre-product and the table 3 in the vertical blender (MTI-Mischtechnik Industrieanlagen GmbH, model LM1.5/5) and under 750rpm, apply with 40g 25wt% ethylene carbonate solution.

Coated pre-product is transferred to Gericke powder conveyer (Gericke GmbH, model GLD75) is sent to continuously in the Labor-Nara reactor (HTM Reetz GmbH, model is laboratory arm mixer " Mini-Nara II ") in and with the conveyer performance of 20g/min.The time of staying in exsiccator is about 90 minutes and product is heated to 185-195 ℃ maximum temperature.During this period, the fusing of secondary cross-linking and described thermoplastic adhesives taking place, influences flow behavior and self is distributed on the surface.

Table 3

Embodiment shows the use by thermoplastic adhesives, other fine particles of following the superabsorbents fine particle of described water absorbent polymer and being different from described water absorbent polymer can be bonded on the water-absorbing polymeric particles with the dust ratio of high stability and reduction, and can not make the absorbent properties such as the reserve capability or mobile impaired of the water-absorbing polymeric particles that so obtains.

Claims

1. powdery, water-absorbent polymers, it comprises as component:

The particle diameter of-0.01-20wt% is less than the fine particle of 200 μ m,

The thermoplastic adhesives of-0.001-10wt%,

The particle diameter of-60-99wt% is 200 μ m and above water-absorbing polymeric particles,

Wherein

Described fine particle is bonded on the surface of described water-absorbing polymeric particles by thermoplastic adhesives and described powdery, water-absorbent polymers has arbitrary following properties:

The flow valuve FFC of-1-13, or

-be at most 6 dust ratio.

2. the powdery, water-absorbent polymers of claim 1, it has the flow valuve FFC of 1-13 and is at most 6 dust ratio, respectively based on the gross weight of described powdery, water-absorbent polymers.

3. claim 1 or 2 powdery, water-absorbent polymers, wherein said thermoplastic adhesives have at least 50 ℃ the fusion temperature according to ISO 11357.

4. the powdery, water-absorbent polymers of claim 1, wherein said thermoplastic adhesives are according to Brookfield, and ASTM E 28 adopts the melt viscosity of No. 27 rotors less than 2000Pas under 160 ℃ temperature.

5. the powdery, water-absorbent polymers of claim 1, wherein said thermoplastic adhesives comprise the condensation polymer of 10wt% at least.

6. the powdery, water-absorbent polymers of claim 5, wherein said condensation polymer is a polyester.

7. the powdery, water-absorbent polymers of claim 1, wherein said fine particle comprises organic fine particle of 80wt% at least in the weight of this fine particle.

8. the powdery, water-absorbent polymers of claim 1, wherein said fine particle comprises the inorganic fine particle of 80wt% at least in the weight of this fine particle.

9. the powdery, water-absorbent polymers of claim 1, wherein these water absorbent polymers carry out secondary cross-linking by surface crosslinking agent at surf zone.

10. the powdery, water-absorbent polymers of claim 9, wherein said surface crosslinking agent comprises at least a organic compound or at least a multivalent metal cation.

11. powdery, water-absorbent polymers, it comprises crosslinked, the neutral polyacrylic acid of part of 30wt% at least, and has at least a following performance

The flow valuve FFC of P11-13; Or

P2 is at most 6 dust ratio;

The abrasion index A of P31-17 _i

The wearing and tearing difference A of P40-7 _d

P5 is the reserve capability according to ERT441.1-99 mensuration of 20g/g at least.

12. the preparation method of powdery, water-absorbent polymers, wherein will be as composition:

The particle diameter of-0.01-20wt% is less than the fine particle of 200 μ m,

The thermoplastic adhesives of-0.001-10wt%,

Under 120-250 ℃ temperature, be in contact with one another.

13. the method for claim 12, wherein said contact is carried out in the holding furnace of carrying continuously.

14. the method for claim 13, the conveyer device that wherein said stove and accessory has movably, heated.

15. each method among the claim 12-14 wherein makes the secondary cross-linking agent contact with defined component in the claim 12.

16. the method for claim 15, wherein said secondary cross-linking agent and described thermoplastic adhesives are added in other compositions together.

17. the method for claim 15, wherein described at least secondary cross-linking agent is present in the liquid phase.

18. powdery, water-absorbent polymers, it obtains by each method among the claim 12-17.

19. the powdery, water-absorbent polymers of claim 18, it has the performance P1-P5 of definition at least a claim 11.

20. the powdery, water-absorbent polymers of claim 1 or 18, wherein the described powdery, water-absorbent polymers of 50wt% has particle diameter greater than the scope of 50 to 2,000 μ m at least.

21. transmission method, wherein claim 1 or 18 powdery, water-absorbent polymers flow through passage.

22. the transmission method of claim 21, wherein said passage be configured for producing water absorbent polymer equipment a part or be used for the part of the metering system of water absorbent polymer.

23. complex, it comprises the powdery, water-absorbent polymers of claim 1 or 18.

24. chemicals, it comprises the powdery, water-absorbent polymers of claim 1 or 18.